Mannich reaction compounds



Patented Aug. 17, 1954 James*M.-Spra;gue, Drexel Hill, Pa assig'ilor' to Merck & 00., Inc., a corporation of New'Jersey NbDrawing. Application August 31,1949, Serial No. 113,496

3 Claims. (Cl. 260-5567 .6)

This invention: is concerned broadly with new quaternary ammonium salts. It is more" particularly concerned with the quaternized salts of tertiary amines, which amines are' obtained-by reacting aryl-alkyl ketones according to the Mannich reaction. Further, the invention is also parti'cularly concerned with l the quaternary salts of the tertiary amines obtained ibyconvertingtthe ketonic group of the amines obtained by the Mannichreaction to acarbinol or methylene group.

The new compounds embraced by this invention can 'berepresented by thegeneral formula inwhichRfis hydrogen'or" a substituted or un substituted alkyl radical containing up to sixteen carbonatoms, R is lower alkyl, R is a lower alkyl radical or a" saturated or unsaturated aralkyl radical containing, less than '18 carbon atoms, X is an anion, such as, forexample, halide, sulfate, sultonatepacetate, and 'ingeneral the anions 'of the usual rquaternizing agentsi Y ishydrbgen oran alkyl group containing less than 20*carbonatorn's; n is one, two or three; and Z represents the remaining valences of the-alpha carbonatom of the benzyl group, which may be satisfied by oxygen -when ketonic, by hydrogen and a hydroxyl group when carbinol, andby two hydrogen atoms when methylene. These new quaternary ammonium compounds exhibit bactericidal and germicidal action and are useful as :suchagents, for example for sterilizing, fortreatment of cutsand wounds, for use as a gargle, and for other therapeutic uses. The unquaternized compounds are useful as intermediates andhave application as-therapeutic agents.

The keton-iccompounds represented by the general formula B R+OH'-'OHzN in which the various'symb'ols have the significance above referred to; are preferred by reacting various aryl alky l ketones with formaldehyde and a secondary aminein an acidic medium accord-- ing tothe Mannich reaction. Particularly suitable aryl alkyl ketones are-decanophencne, undecanophenone;dodecanophenone, and nuclearlyalkyl-substitutedacetopheriones. Dimethylamine is an example of a suitable Secondary amine. The quaternary ammonium salts of the resultant ketonic tertiary arriinesexhibit bactericidal and germicidal'actiyity, 'althoug'h 'their life span in aqueous solution is cremated duration because of decomposition.

Aryl alkyl ketones-suitableior reaction with formaldehyde" anddimethylamine to produce ketonic tertiary amines are, for example, hexanophenone; octanop'henone, non'anopheno ne, de-

p h e n on e, tetraclecanophenone, p-hexylacetophenone, p-dodecylacetophenone, p-tetradecylacetophenone, p-octyl-propio'phenone, omega-cyclohexylalkyl phenyl ketones, p-hexylhexanophenone, p butylh'eptanophenone; These ketones on reactionwith formaldehyde and dimethylamine yield the tertiaryamines, (Z-benzoylhexyl) -di-methyla'mine,' (2- be'nzoyloctyl) dimethylamin; 2-benzoylnonyl)--dimethylamine, (2- benzoyldecyl) dimethylamine; 2 benzoylundecyl) dimeth'ylamine (2 benzoyldodecybdimethylamine, (Z-benZoyItetradecyI-"Jdimethyh amine, (2-p-hexylbenzoylethyl) -dimethy1amine, (2 p dodecylbenzoyl ethyl) dimethylamine, (2 ptetradc'cyibenzoyl ethyl) dimethylamine, (2 p octylbenzoyl propyli dim eth ylamine, (2 benzoyl omega cyclohexyl alkyl) -dimethyl amine's', (2 p-hexylbenzoyl hexyl) dimethylamine," and 2-p buty1benzoyl-heptyl) dimethylamine, It is to be notedthatthe compounds with diand trif-alkyl substituents in the benzoyl nucleus aresuitable as well as the monoalkyl substituted compounds;

The above compounds arefuseful in the preparation of the carbinoland methylene-type tertiary amines, and further, because of the known instability of the tertiary amines and corresponding quaternary ammonium salts, can be used to obtain the vinylcomp'ounds by decomposition and 'loss of the nitrogen grouping.

Starting with the above named aminoketones, various alcohols are obtained by converting the hydrochlorides of the amin'oketones to the correspondingalcohols by catalytic hydrogenation, for example, by using a palladium-on-charcoal catalyst. Theamin'o alcohols are isolated either as the hydrochlorides or as"the"freebases, the

bases being in general colorless oils and stable to distillation.

Starting with the appropriate ketones, by hydrogenation there can be obtained various desired alcohols, for example, (2-oi-hydroxybenzylhexyl) dimethylamine, (2 a hydroxybenzyloctyl) dimethylamine, (2 or hydroxybenzyldecyl) -dimethylamine, (2-oc-hYdI'OXYb6I1ZY1-L1I1- decyl) dimethylamine, (2 a hydroxybenzyldodecyl) dimethylamine, (2 oz hydroxybenzyltetradecyl)-dimethylamine and [2-(oc-hYdI0XY- are hydrogenation of the acetate of the appropriate carbinol in the presence of palladium-char- .coal catalyst, and hydrogenation of the appropriate carbinol in the presence of copper chromite catalyst at approximately 200 C.

By similar methods of hydrogenation there were obtained, by starting with the appropriate carbinol compound, such compounds as 2-benzyltetradecyl-dimethylamine, (3-p-dodecylphenylpropyl -dimethylamine and (3-p-tetradecylphenylpropyl)-dimethylamine. The hydrochlorides of these compounds exhibit germicidal and bactericidal action in solution and further the compounds are useful in the preparation of their quaternary ammonium salts.

The various ketonic, carbinol, and methylene type compounds above described are quaternized by reaction with the usual quaternizing compounds to produce bactericidal and germicidal compounds. Particularly effective quaternary ammonium salts are derived from benzyl and cinnamyl quaternary halides.

Starting with the respective ketonic, carbinol, or methylene compounds, obtainedas above described, on reaction with a quaternizing agent, for example, benzyl ,or cinnamyl chloride or methyl iodide, there are obtained, for example, such compounds as:

(2-benzoyldodecyl) trimethy1 ammonium iodide (Z-benzoyldodecyl) -dimethyl benzyl ammonium chloride Benzoyl-tetramethylammonium iodide (Z-a-hYdIOXYbEIlZYl hexyl) dimethyl benzylammonium chloride (2-04-11YdI'OXYbBI1ZY1 octyl) dimethyl benzylammonium chloride (2-a-hydroxybenzyl-octyl) -dimethyl cinnamylammonium chloride (2-a-hydroxybenzyl-decyl) -dimethyl-benzyl-ammonium chloride (2-a-hydroxybenzyl-decyl) -dimethyl cinnamylammonium chloride (2-a-hydroxybenzyl-undecyl) -dimethyl benzylammonium chloride (2-a-hydroxybenzyl-undecyl) dimethyl cinnamyl-ammonium chloride (2-oc-hYdIOXYbBIlZYl-dOdBCYl) -dimethyl benzyl ammonium chloride (2-oc-hYdI'OXYbGIlZYl-dOdGCYD -dimethyl-cinnam yl-ammonium chloride (2-a-hydroxybenzyl-tetradecyl) -dimethyl-benz yl-ammonium chloride (2-or-hydroxybenzyl-tetradecyl) dimethyl cinnamyl-ammonium chloride [2- (oL-hydroxy-p-octylbenzyl) -propyl] -dimethylbenzyl-ammonium chloride [2- (a-hydroxy-p-octylbenzyl) -propyl] -dimethylcinnamyl-ammonium chloride [2- (a-hydroxy-p-butylbenzyl) heptyl] -dimethyl benzyl-ammonium chloride [2- (oc-hYdlOXY-D-blltYlbBllZYl) -heptyll dimethyl-cinnamyl-ammonium chloride [2-(oc-1'1YdI'OXYb8I1ZY1) -3-cyclohexyl-propyll dimethyl benzyl-ammonium chloride EZ-(d-hydroxybenzyl) 4-cyclohexyl butyll dimethyl-benzyl-ammonium chloride [2-(a-hydroxybenzyl) -4cyclohexyl butyll dimethyl-cinnamyl-ammonium chloride [2- (a-hydroxybenzyl) -5-cyclohexyl pentyl] -dimethyl-benzyl-ammonium chloride [2- (or-hydroxybenzyl) -5cyclohexyl pentyll-dimethyl-cinnamyl-ammonium chloride (Z-benzyl-dodecyl) -dimethyl-benzylammonium chloride, and (Z-p-dodecylbenzyl-propyl) diinethyl benzylammonium chloride It is apparent from the above that the substituted alkyl portion of the quaternary amine can consistof as few as two carbon atoms, for example, when the starting material is acetophenone, and that the chain can be of considerable length as, for example, when the starting material is tetradecanophenone.

It is to be realized that the portion of the molecule indicated by the symbol R in the general formula can be a substituted alkyl radical, for instance, aralkyl or cycloaliphatic-substitutedalkyl, as, for example, when Z-cycIoheXylethyl phenyl ketone is used for the starting material. Further, the alkyl radicalcan be saturated or unsaturated, and straight or branch chain.

The invention is illustrated by, but not necessarily limited to, the following examples:

Eatample 1.Preparation of (Z-beneoylundecyZ) dimethylamine ihydrochloride.Into a one liter flask equipped with a reflux condenser was placed 51 grams (0.207 mole) of undecanophenone, 7.08 grams (0.079 mole) of paraformaldehyde, 18.55 grams (0.228 mole) of dimethylamine hydrochloride, and 104 ml. of anhydrous ethyl alcohol to which had been added six drops concentrated hydrochloric acid. The mixture was refluxed for approximately hours. At three intervals, the refluxing was interrupted long enough to add 1.44 grams of paraformaldehyde and 4 grams of dimethylamine hydrochloride. At the end of the heating period the solvent was removed by evaporation at room temperature in a current of air. The residue was titurated with isopropyl ether until a test portion was completely soluble in water. The product waspurified by recrystallization from boiling water. The product, (2-benzoylundecyl)-dimethylamine hydrochloride, M. P. 133-134 C. uncorr., was obtained in 57% of the theoretical yield.

Other examples of the preparation of Mannich ketone hydrochlorides are illustrated below. The indicated starting ketone is treated according to a procedure similar to that outlined in Example 1 and by use of similar molar proportions to yield the indicated Mannich ketone. The reaction time will vary between approximately ten and one'hundred and twenty hoursdependingon the particular reactants. In general, the completion of thereaction is indicated by relatively complete solubility of a test portion in water.

M. PL, Starting'Matcrial Compound Obtained 0.,

1 ,uncorr.

p-dodecylacetophe- (2-p dodecylbenzoyl ethyl) 142-142. 6

none; dimethylarnlne hydrochloride. j p-octylphenyl ethyl (2 p octylbenzoyl propyl) 130-140 ketonc. dimethylemine hydro chloride. 2 cyclohex y 1 e th y 1 (2-1)enzoyl-3-cyclohexyl propyl) 181-182 phenyl ketone. dimethylamine hydrochloride. Hexanophenone 2 benzoylhexyl) dimethyla- 129. 5-130 mine hydrochloride.

p-hu'tylphenyl hexyl (2 p butylbenzoylheptyl) di- 108-109 ketone. methylamme hydrochloride. Octanophcnone. 2 benzoyloctyl) dimethyla- 130-131 mine hydrochloride. Decanophenone (2 benzoyldecyl) dirnothyla- 129-130 Dodccanophenonc (Z-benzoyldodecyl) dimethyla- 131-132 mine hydrochloride. 'Ie'trad'ecanoplienone (2-benzoyltetradecyl)-ditnethyl 130. 5-131 amine hydrochloride. 1

All. of. the above indicated starting materials are known except Z-cycilohexylethyl phenyl ketone. This ketone was prepared as follows:

1 56 grams (1.0 mole)- of 3cyclohexylpropionic acid: was treated with 154.7 gm- (1.3 moles) of Example 2.-Prcparatz'on of (2 ben'eoyldo decyl) -dimethyZaminc.--24.2'8 gm. of (2-benzoyl dodecyl) -dimethylamine hydrochloride (obtained as in Example 1) was disolved in 200 ml. water at room temperature. The solution was made al.- kaline with a slight excess of sodium hydroxide and then saturated with sodium chloride. The free base was precipitated as an oil. The oil was extracted from the water phase with '75 ml. isopropyl ether. The ether solution was washed five times with water, dried over anhydrous sodium sulfate and filtered. The ether was removed under vacuum at room temperature. The residue was dried in vacuo over concentrated sulfuric acid. There was obtained 18.59 gm. of (Z-benzoyldodecyl) -dimethylamine, n 1.4940. 1

Example 3.- Prepamtion of (Z-a-hydrorybenzyl-undccyl)-dimethyZamine.A one liter three-necked flask was equipped with a mercuryfilled stirrer and each side neck closed with a neoprene stopper fitted with a glass stopcock. Air in the flask was replaced with nitrogen. Into the flask was placed 34 grams (0.10 mole) of (2- benzoylundecyl)-dimethylamine hydrochloride (obtained as in Example 1), 9.2 grams palladium (10%) on charcoal catalyst, and 500 ml. of anhydrous denatured ethyl alcohol. The nitrogen was replaced with hydrogen. Both stopcocks were closed and one was then connected with a A mixture of 714.6 gms. (9.16 moles) of benzene and 158.7 gms. (1.19 mole) of aluminum chloride were stirred together a fiask, equipped with a dropping funnel and a reflux condenser, on-a steam bath. There was added dropwise over aperiod of about one hour 160 gms; (0.916 mole) 1 The mixture 3-cyclohexylpropionyl chloride. was refluxed for one and one-half hours after which it was hydrolyzed with a mixture of conhydrogen buret and that stopcock op-ened. A stirrer was started and the reduction allowed to proceed until 0.10 mol (1 molar equivalent) of hydrogen was taken up.

The reaction mixture was filtered to remove the catalyst. The filtrate was evaporated in a current of air until most of the alcohol was removed.

The residue was dissolved in approximately 600 ml. of water and made alkaline with an excess of 28% ammonium water, whereupon the base separated as an oil. The base was dissolved in benzene, washed three times with water and distilled under reduced pressure. The distillate between 187-188 C. at about 2 mm. pressure was collected. The product, (2-ov-hYdI'OXYbEIlZYl-lllldflfll)-dimethylamine, was obtained in 81% of the theoretical yield.

Other examples of the preparation of Mannich alcohols are illustrated below. The indicated starting ketone is reacted according to a procedure similar to that outlined in Example 2 and in similar molar proportions, to yield the indicated Mannich al-cohol:

Starting Material Phys. Constants (2-p-dodecylbenzoyl-ethyl)-din1ethylamine .1

(2-p-oc'tylbcnzoyl-propyl) -din1ethylamine (Z-benzoy1-3-cyclohexyl-propyl)-dimethy1amine (z-benzoyl-hexyl)-dimethylamme (2-p-buty1-benzoyl-heptyl) -dimethylamine -1 (2-benzoyl-octyl)-dimethylarnine (2-benzoyl-decyl)dimethylamine z-benzoyl-dodecyl)oimethyIamine o (fl benzoyl-tctradecyl)-dimethy1amine [2-(oz-hydroxy-p-dodccylbenzyl)-ethyl]-dirnethylamine [2- (u-hydroxy-p-octylbcnzyl) -propyl1-dimethy1a1nine [2-(a-hydroxybenzyl) -3-cyclohexyl-propyl]-dimcthylamine M. P., hydrochloride,

B. P. 176-178 C. at

M. P. 104-106 C.

Starting with the appropriate cyclohexylalkanoic acid, it is possible, by a series of reactions similar to those just described, to prepare various omegarcyclohexylalkyl phenyl ketones, for example; 3-cyc1ohexylpropyl phenyl ketone, 4-cyclohexylbutyl phenyl ketone, and 5-cyclohexylpentyl: phenyl ketone.

Example 4.-Prcpamtion of Z-benzyldorlecyldimethylamina-lnto a 200 ml. flask equippedwith reflux condenser was placed a mixture of 35.6 grams (0.10 mole) of (z-a-hydroxybenzyldodecyD-dimethylamine hydrochloride (obtained as inExarnple 2) and 40.8 grams (0.40 mole)= of acetic anhydride, which was gently warmed to aesasos refluxing and gentle refluxing maintained during 2 19, hours. The mixture was poured into a beaker and allowed to cool. On cooling there was obtained a thick mass of crystals which was collected on a Buchner funnel, washed with a little absolute ethyl acetate and recrystallized from boiling anhydrous ethyl alcohol. There was obtained (2 c acetoxybenzyl dodecyl) diznethylamine hydrochloride in 78% of the theoretical yield, M. P. 190-191 C. uncorr.

The palladium-charcoal catalyst used in the hydrogenation step was prepared as follows:

100 ml. of a solution of palladium chloride, 100 gm. of decolorizing charcoal, and 500 ml. of distilled water were stirred together for approximately ten minutes. With continued stirring a solution of 272 gm. moles) of sodium acetate in 500 ml. of distilled water was added. The mixture was then stirred in an atmosphere of hydrogen until hydrogen was no longer taken up.

The catalyst was separated on a Buchner funnel, washed with distilled water until the washings gave a neutral reaction, and then dried by heating at a temperature substantially above 100 C. until all water vapor was driven off and the catalyst became a free flowing powder,

It is particularly to be noted that this palladium-charcoal catalyst can be very pyrophoric and accordingly should be handled carefully.

The acetylated Mannich alcohol obtained as described above was reduced to obtain the desired methylene compound, as follows:

23.88 grams (0.060 mole) of the acetylated Mannich alcohol, 20 grams of palladium catalyst (obtained as above described and equivalent to 2 grams palladium) and 500 ml. anhydrous ethyl alcohol were stirred in an atmosphere of hydrogen until the theoretical amount of hydrogen was taken up. This process required approximately 3 hours. The catalyst was separated by filtration and the filtrate evaporated to dryness at room temperature. The residue was dissolved in water and the solution made alkaline with 60 ml. of 28% ammonium water. The oil that separated was then dissolved in 100 ml. of benzene, washed three times with water and distilled under reduced pressure. The product obtained was 2- benzyldodecyl-dimethylamine, a colorless liquid. B. P. 177180 C. at approximately 2 mm. pressure. The yield was 12.5 grams (68% of theoretical). The melting point of the amine hydrochloride is 103-104. C.

Example 5.Prepamtion of Z-benzyldodecyldimethylamine hydrochloride-3.33 grams (0.0104 mole) of (2-a-hydroxybenzyldodecyl)-dimethylamine, 3 grams of copper chromite catalyst, and 75 ml. of anhydrous ethyl alcohol were placed in a hydrogenation bomb. Hydrogen was added to a pressure of approximately 1500 lbs. per square inch at room temperature. The bomb temperature was raised to, and maintained at, approximately 200 C. and the pressure was then observed to be approximately 2400 lbs. per square inch. At the end of seven hours the bomb was allowed to cool. The reaction mixture was removed from. the bomb and the alcohol evaporated in a stream of air. The residue was an oilybase, which was converted into the hydrochloride by reaction with hydrochloric acid and then dried. The yield of the crude hydrochloride was 2.6 grams (73% of theoretical yield). on recrystallization from boiling absolute ethyl alcohol, the hydrochloride melted at 103.5104.5 C. (uncorr.)

The mixed melting point of this hydrochloride 8 with the hydrochloride obtained as in Example 4 was 103-104 C.

Example 6.-Preparation of (3-p-dodecylphenyl-propyl)-dimethylamine hydrochloride.- 2.7 grams (0.0071 mole) of (2-p-dodecylbenzoylethyl) -dimethylamine hydrochloride (obtained as in Example 1), 2.0 ml. concentrated hydrochloric acid, 198 mls. of water and 3.0 grams of palladium-charcoal catalyst were shaken overnight in an atmosphere of hydrogen. The catalyst was removed by filtration, the filtrate evaporated, and the residue recrystallized from benzene and hexane. The product was recrystallized from a mixture of isopropyl ether and anhydrous ethyl alcohol denatured with 5% benzene, yielding 0.70 gram of (3-p-dodecylphenylpropyl)-dimethylamine hydrochloride, M. P. 185.5487 uncorr.

Exalmple 7.Preparation of (Z-beneoyldodecyl)dimethyl-benzyZ-ammonium chloride-6.35 grams (0.02 mole) of (Z-benzoyldodecyl) -dimethylamine (obtained as in Example 2), and 2.35 grams (0.02 mole) benzyl chloride were mixed together and allowed to stand at approximately ISO-35 C. until a test portion of the solid product was completely soluble in water. The product (2-benzoyldodecyl) -dimethyl benzyl-arnmonium chloride, was a glassy solid. An aqueous solution of the material as prepared was tested for bactericidal activity and found to be effective.

Example 8.Preparatzon of (Z-benzoyldodecyl) trimethyl ammonium iodide.2.3 grams (0.0072 mole) of (Z-benzoyldodecyl)-dimethylamine (obtained as in Example 2), and 1.02 grams (0.0072 mole) methyl iodide were mixed together in a flask. The reaction mixture became warm almost at once and after about two minutes was quite viscous. The flask was stoppered and the mixture was allowed to stand overnight at approximately 30-35 C. An aqueous solution of the crude material was testedfor bactericidal activity and found to be effective.

Example 9.-Preparation of (Z-a-hydTOrybenzyl undecyl) dimethyl cimmmylammonium chloride-10.69 grams (0.035 mole) of (Z-ahydroxybenzyl undecyl) dimethylamine (obtained as in Example 3), and 5.34 grams (0.035 mole) cinnamyl chloride were placed in a stop pered glass flask and the mixture thoroughly shaken. It was then allowed to stand at room temperature for four days until a test portion of the solid product was completely soluble in water. The crude reaction product was recrystallized from a boiling mixture of anhydrous ethyl alcohol and absolute ethyl acetate. There was obtained (2 0c hydroXybenzyl-undecyl) -dimethyl-cinnamyl-ammonium chloride, M. P. -186 C. uncorr. in 69% yield. 1

Example 10.-Preparation of (2-a-hydroacybenzyZ-dodecyl) dimethyl beneylammonium chloride-4.23 grams (0.0132 mole) of (Z-a-hYCll'OXY- benZyl-dodecyl)-dimethylamine (obtained as in Example 3), and 1.67 grams (0.0132 mole) benzyl chloride were mixed in a stoppered flask and allowed to stand at approximately 3035 C. for

mine (obtained as in Example 3), and 1.14 grams nary ammonium salts of the carbinol type tertiary amines obtained as in Example 3 are illustrated below. The quaternary ammonium salts listed below are obtained by reacting molar quantitles of the appropriate tertiary amine with the appropriate quaternizing agent according to the procedures outlined in Examples 9, and 11.

M. P., C.,

Quaternary Ammonlum Salts Uncom (z-whydroxybenzyl hexyl)-dimethyl-benzyl-ammonium choride (2-a-hydroxybenzyl octyl)-dimethyl-benzyl-ammonium chloride (2-a-hydroxybenzyl octyD-dirneth lmonium choride (2-a-hydroxybenzyl um chloride (Z-a-hydIoXybenZyl decyl)-dimethy1-cinnamyl-ammonium chloride (2-a-hydroxybenzyl undecyl)-dimethyl-benzyl-ammonium choride. (2-a-hydroxybenzyl dodecyl)-dimethyl-cinnamyl-ammonium chloride (z-a-hydroxybenzyl tetradecyl)-dimethyl-benzy1-ammonium chloride (Z-a-hydrOXybenzyl tetradecyl)-dimethyl-cinnamylammonium chloride [2-(or-hydroxy p butylbenzyl) -heptyl] dimethyl-bcnzyl-ammonium choride 2-(a-hydroxy p butylbenzyl) heptyl] dimeth l-cinmethyl-ammonium chloride [2-(a-hydroxy-p-octy1benzy1)-propyl1-dimethyl enzylammonium chloride [2-(a-hydroxyb enzyl) 3 cyclohexyl propyl] dimethylbenzyl-ammonium chloride [2-(a-hydroxybenzy1) 3 cyclohexyl propyl] dimethylcinnamyl-ammonium chloride Example 12.- Preparation of (Z-beneyldodecyl) -dimethyl benzylmmonium chloride-5.16 grams (0.17 mole) of 2-benzyldodecyl-dimethylamine (obtained as in Example 4) and 2.13 grams (0.17 mole) of benzyl chloride were mixed'and allowed to stand at room temperature until a sample of the product was entirely soluble in water. The product was dissolved in a minimum amount of boiling absolute ethyl acetate and the hot solution diluted to about four times its volume with hexane. as a very viscous oil. When cool, the super- The product came out of solution chloride, together with natant liquid was decanted and the oil dried in vacuum over concentrated sulfuric acid. The dried product (2loenzyldodecyl) -dimethyl-benzyl-ammonium chloride was a very hygroscopic wax, such that it was not possible to obtain a melting point. An aqueous solution of the material was tested for bactericidal activity and found to be effective.

Example 13.--Preparation of (3-p-dodecylphenyl) prop'yl dimethyl :benzyl ammonium chloride-3.68 grams (0.01 mole) of (3-p-do- 1c decylphenyl) -propyl-dimethylamine (obtained by treating the amine hydrochloride obtained as in Example 6 according to a procedure similar to that described in Example 2) and 2.5 ml. benzyl chloride, together with 100 ml. of benzene were mixed in a flask equipped with a reflux condenser. The mixture was refluxed for approximately 70 hours and the benzene removed by vacuum distillation. The residue was dried in vacuo over concentrated sulfuric acid and recrystallized from a mixture of anhydrous ethyl alcohol denatured with 5% benzene and petroleum ether. There was obtained 1.9 grams of (B-p-dodecylphenyl) propyl dimethyl benzyl ammonium chloride, M. P. 65-66 C. uncorr.

It is to be realized that the above examples are illustrative rather than limitative of the scope of the invention and that compounds embraced by the invention can be obtained by substituting for the enumerated reactants their equivalents.

What is claimed is:

in which R is alkyl radical containing from 8 to 12 carbon atoms, R is chosen from the group consisting of benzyl and cinnamyl, and X is an anion.

2. (2 a hydroxybenzyl undecyl) dimethylcinnamyl-ammonium chloride.

3. (2-oa-hfy'dl'0XYbi-ZI1ZY1 dodecyl) dimethylbenzyl-ammonium chloride.

References Cited in the file of this patent UNITED STATES PATENTS Name Date Mettler Mar. 17, 1942 OTHER REFERENCES Number 

